CN113619224A - Low-water-absorption flexible fluorine copper-clad plate and preparation method thereof - Google Patents

Low-water-absorption flexible fluorine copper-clad plate and preparation method thereof Download PDF

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CN113619224A
CN113619224A CN202110833579.XA CN202110833579A CN113619224A CN 113619224 A CN113619224 A CN 113619224A CN 202110833579 A CN202110833579 A CN 202110833579A CN 113619224 A CN113619224 A CN 113619224A
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fluorine
layer
flexible copper
substrate layer
copper
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CN113619224B (en
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张黄平
徐莎
王洋
刘成河
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Zhongshan Allstar Electronic Materials Co ltd
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Zhongshan Allstar Electronic Materials Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09J127/18—Homopolymers or copolymers of tetrafluoroethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Fluid Mechanics (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The application relates to the technical field of flexible copper clad plates, in particular to a low-water-absorption fluorine material flexible copper clad plate and a preparation method thereof. The copper-clad laminate comprises a substrate layer and a copper layer, wherein the upper surface and the lower surface of the substrate layer are coated with fluorine-containing glue layers; the material of the substrate layer is modified polyimide. The preparation method of the flexible copper-clad plate comprises the following steps: (1) preparing glue solution: adding a fluorine-containing compound into a solvent, adding a compound dispersing agent, an inorganic filler and thermoplastic polyimide, and stirring and mixing to obtain a glue solution; (2) coating: coating the glue solution on the upper surface and the lower surface of the substrate layer, and drying the solvent; (3) and (3) sintering: sintering the base material layer coated with the glue solution; (4) and (3) laminating: and carrying out copper foil pressing on the sintered substrate layer to obtain the product. The method is simple to operate, and the fluorine material flexible copper-clad plate prepared by the method has the advantages of excellent dielectric property, high peel strength, high tensile strength, good folding resistance, excellent dimensional stability, good soldering resistance and low water absorption rate.

Description

Low-water-absorption flexible fluorine copper-clad plate and preparation method thereof
Technical Field
The application relates to the technical field of flexible copper clad plates, in particular to a low-water-absorption fluorine material flexible copper clad plate and a preparation method thereof.
Background
The high-frequency fluorine flexible copper clad laminate which is one of key materials in electronic communication and information industry is generally applied to the fields of mobile phones, 5G communication, computers, vending machines, communication base stations, satellites, gradually-emerging wearable equipment, unmanned automobiles, unmanned aerial vehicles, intelligent robots and the like, and is widely concerned by the industry and academia.
In the high-frequency fluorine material flexible copper clad laminate, the water absorption of the dielectric layer is an important index influencing the ion migration resistance of the fluorine material. When the water absorption of the dielectric layer is too high, the copper metal on the circuit board is ionized under a certain condition and migrates from the positive pole to the negative pole of the electric field through the insulating layer (dielectric layer) under the action of the electric field, so that the insulating property is reduced, thereby affecting the working performance of the circuit board, even causing short-circuit accidents, and endangering the life safety of users! On the other hand, when the water absorption of the dielectric layer is too high, the dimensional stability of the flexible copper clad laminate is also greatly affected. At present, although the water absorption of the double-sided fluorine flexible copper clad laminate using MPI as a base material is extremely low, the overall water absorption of the fluorine dielectric layer composite material is relatively high due to the defect of a short board with relatively high water absorption of the MPI base material. In order to solve the problem, the prior art method is as follows: starting from MPI raw materials, hydrophobic functional groups are introduced by a method of blocking or grafting and the like during MPI synthesis, or substances with low water content such as fluorine and the like are added by blending in an MPI forming process, so that the water absorption rate of an MPI base material is reduced. Although the technical method can reduce the water absorption rate of MPI to a certain extent, the surface dyne value of the base material can be reduced to a certain extent, the adhesive force between the base material and the fluorine material is reduced, and the peel strength of the flexible copper clad laminate is further reduced.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the application provides a low-water-absorption fluorine material flexible copper-clad plate which comprises a substrate layer and a copper layer, wherein the upper surface and the lower surface of the substrate layer are coated with fluorine-containing glue layers; the material of the substrate layer is modified polyimide.
As a preferable technical scheme of the invention, the surface tension of the substrate layer is not lower than 60 dyn; preferably, the dielectric loss of the substrate layer is not higher than 0.0045(10 GHz).
In a preferred embodiment of the present invention, the surface roughness Rz of the copper layer is not higher than 1.5 μm.
As a preferable technical scheme of the invention, the thickness of the copper layer is 5-25 μm; preferably, the thickness of the fluorine-containing adhesive layer is 5-50 μm; preferably, the thickness of the base material layer is 5-80 μm.
The second aspect of the application provides a preparation method of the low water absorption fluoride material flexible copper clad laminate, which comprises the following steps:
(1) preparing glue solution: adding a fluorine-containing compound into a solvent, adding a compound dispersing agent, an inorganic filler and thermoplastic polyimide, and stirring and mixing to obtain a glue solution;
(2) coating: coating the glue solution obtained in the step (1) on the upper surface and the lower surface of the base material layer, and drying the solvent; preferably, the temperature in the coating is 120-180 ℃; preferably, the linear speed of the coating is controlled to be 2-5 m/min;
(3) and (3) sintering: sintering the base material layer coated with the glue solution in the step (2), wherein the sintering temperature is 100-380 ℃;
(4) and (3) laminating: carrying out copper foil lamination on the substrate layer sintered in the step (3), wherein the lamination temperature is 320-360 ℃, and the lamination pressure is not lower than 3Mpa, so as to obtain the low-water-absorption fluorine material flexible copper clad laminate; further preferably, the dwell time in the pressing is not less than 15 min.
In a preferred embodiment of the present invention, the fluorine-containing compound is one or more selected from the group consisting of polytetrafluoroethylene, a copolymer of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene, a tetrafluoroethylene-perfluoromethyl vinyl ether copolymer, and an ethylene-tetrafluoroethylene copolymer.
As a preferred technical solution of the present invention, the thermoplastic polyimide molecular structure contains at least one of an imide group, an ether group structure, and an alkyl group structure; preferably, the viscosity of the thermoplastic polyimide is 20000 to 40000 cps.
As a preferable technical scheme of the invention, the raw materials for preparing the thermoplastic polyimide comprise 1, 3-bis (3-aminophenoxy) benzene and/or 1, 3-bis (4-aminophenoxy) benzene, bisphenol A type diether dianhydride and/or 4,4' -oxydiphthalic anhydride.
As a preferable technical scheme of the invention, the inorganic filler is selected from one or more of nano-silica, silicon micropowder, molybdenum disulfide and carbon fiber; preferably, the particle size is not higher than 10 μm; preferably, the surface is coated with a silane coupling agent.
As a preferred technical scheme of the invention, the sintering process in the step (3) comprises a preheating process, a high-temperature sintering process and a cooling annealing process; the temperature of the high-temperature sintering process is more than or equal to 315 ℃, and the high-temperature sintering time is not less than 15 min.
Has the advantages that: in the application, inorganic filler coated by a silane coupling agent is added into a glue solution raw material, the filler has good compatibility in a fluorine-containing compound (polymer resin), the roughness between a fluorine material (namely a fluorine-containing glue layer) and an MPI (substrate) interface can be increased by the filler, specific inorganic filler with high surface energy, easy bonding and the like is added in a high-temperature melting process (comprising a sintering stage and a pressing stage), an easy-bonding modified layer is formed on the surface of the fluorine material after cooling, the interface bonding force between the fluorine material and the MPI of the substrate and between the fluorine material and a high-frequency copper foil is increased, the interface compactness is improved, the contact area between the MPI and external water molecules is reduced, and the water absorption of an integral dielectric layer is reduced. In addition, in the application, the thermoplastic polyimide polymer synthesized by the fluorine-containing dianhydride monomer is added into the fluorine-containing compound (polymer resin), so that the dielectric constant and the dielectric loss are low, the water absorption rate is extremely low, and meanwhile, the structural characteristics of the thermoplastic polyimide further enhance the adhesion of the mixed resin and reduce the porosity among the interfaces of the composite material, so that the water absorption rate of the fluorine material dielectric layer is effectively reduced.
Drawings
FIG. 1 is a schematic structural diagram of a low-water-absorption fluorine material flexible copper-clad plate in the invention.
Wherein: 1-upper copper layer, 4-lower copper layer, 5-upper fluorine-containing adhesive layer, 6-base material layer and 7-lower fluorine-containing adhesive layer.
Detailed Description
The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
It should be understood that other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.
The meaning of "up and down" in the present invention means that when the reader faces the drawings, the upper side of the reader is the upper side, and the lower side of the reader is the lower side, and is not a specific limitation to the mechanism of the apparatus of the present invention.
When a component, element, or layer is referred to as being "on," "bonded to," "connected to," or "coupled to" another element or layer, it may be directly on, bonded to, connected to, or coupled to the other element, or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being "directly on," "directly coupled to," "directly connected to" or "directly coupled to" another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a similar manner (e.g., "between.. versus" directly between.. versus, "" adjacent to "directly adjacent to," etc.). As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The first aspect of the application provides a low-water-absorption flexible copper-clad plate made of fluorine materials, which comprises a substrate layer and a copper layer, wherein the upper surface and the lower surface of the substrate layer are coated with fluorine-containing glue layers; the material of the substrate layer is modified polyimide.
In some preferred embodiments, the surface tension of the substrate layer is not less than 60 dyn; preferably, the dielectric loss of the substrate layer is not higher than 0.0045(10 GHz); further preferably, the dielectric constant of the base material layer is not higher than 3.6(10 GHz); more preferably, the tensile strength of the material of the base material layer is more than or equal to 200 MPa. The properties of dielectric loss, dielectric constant, etc. described herein are determined by methods known to those skilled in the art, and may be determined, for example, by testing according to the GB/T15022.2-2007 standard. The surface tension of the present application was measured using a surface tension meter according to conventional methods.
In some preferred embodiments, the copper layer has a surface roughness Rz of not higher than 1.5 μm; further preferably, the surface roughness Rz of the copper layer is not higher than 1.0 μm. The surface roughness described in the present application is a physical quantity that characterizes the degree of surface roughness of a material, and can be measured according to a conventional method in the art.
In some preferred embodiments, the copper layer has a thickness of 5 to 25 μm; preferably, the thickness of the material is 10-15 μm; preferably, the thickness of the fluorine-containing adhesive layer is 5-50 μm; preferably, the thickness of the fluorine-containing adhesive layer is 20-30 μm; preferably, the thickness of the substrate layer is 5-80 μm; preferably, the thickness of the base material layer is 20-30 μm.
The second aspect of the application provides a preparation method of the low water absorption fluoride material flexible copper clad laminate, which comprises the following steps:
(1) preparing glue solution: adding a fluorine-containing compound into a solvent, adding a compound dispersing agent, an inorganic filler and thermoplastic polyimide, and stirring and mixing to obtain a glue solution;
(2) coating: coating the glue solution obtained in the step (1) on the upper surface and the lower surface of the base material layer, and drying the solvent;
(3) and (3) sintering: sintering the base material layer coated with the glue solution in the step (2), wherein the sintering temperature is 100-380 ℃;
(4) and (3) laminating: and (4) carrying out copper foil laminating on the substrate layer sintered in the step (3) to obtain the low-water-absorption fluorine material flexible copper-clad plate. The low-water-absorption flexible copper clad laminate is prepared by respectively coating a layer of fluoropolymer on two surfaces of a modified polyimide film (MPI) substrate, then sequentially drying and sintering at high temperature in an online Infrared (IR) furnace to obtain a fluorine composite dielectric layer, and finally performing high-temperature pressing on the fluorine composite dielectric layer and a high-frequency copper foil in a high-temperature and high-pressure environment by using uniform-pressure continuous pressing equipment.
<Preparation of glue solution>
The glue solution in the application mainly comprises fluorine-containing compounds, solvents, compound dispersants, thermoplastic polyimide, inorganic fillers and the like.
In some embodiments, the fluorochemical is selected from one or more of Polytetrafluoroethylene (PTFE), a copolymer of perfluoropropyl perfluorovinyl ether and Polytetrafluoroethylene (PFA), polytetrafluoroethylene propylene (FEP), a tetrafluoroethylene-perfluoromethyl vinyl ether copolymer (MFA), an ethylene-tetrafluoroethylene copolymer (ETFE).
Further preferably, the copolymer of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene has a melt flow rate of 18 to 25g/10min (measured according to a conventional method). The fluorine-containing compound can be obtained from commercial products, such as DS705 from China, with melt flow rate of 21.2g/10min and water content of less than or equal to 0.008%.
The solvent used in the glue solution preparation process is not particularly limited, and any solvent known to those skilled in the art may be used, including but not limited to N-methylpyrrolidone (NMP).
The compound dispersant in the present application is a dispersant containing a fluorine compound, and the specific selection thereof is not particularly limited, and various dispersants known to those skilled in the next step can be used, such as a product of Dingjin brand FT-71FL, a solid content of 48.9%, and a specific gravity of 1.092.
In some embodiments, the thermoplastic polyimide molecular structure comprises at least one of an imide group, an ether group structure, and an alkyl group structure; more preferably, the structure of the compound contains a double-part A structure; preferably, the viscosity of the thermoplastic polyimide is 20000-40000 cps; more preferably, the viscosity of the thermoplastic polyimide is 30000 to 40000 cps.
In some preferred embodiments, the raw materials for preparing the thermoplastic polyimide include 1, 3-bis (3-aminophenoxy) benzene (TPE-M) and/or 1, 3-bis (4-aminophenoxy) benzene (TPE-R), bisphenol a type diether dianhydride (BPADA) and/or 4,4' -oxydiphthalic anhydride (ODPA). Namely, the diamine is obtained by reacting any one or two of diamine 1, 3-bis (3-aminophenoxy) benzene and 1, 3-bis (4-aminophenoxy) benzene with any one (or two) of dicarboxylic anhydride bisphenol A type diether dianhydride and 4,4' -oxydiphthalic anhydride.
In some preferred embodiments, the method of preparing the thermoplastic polyimide comprises the steps of:
(1) completely dissolving weighed 1, 3-bis (4-aminophenoxy) benzene (TPE-R) and 1, 3-bis (3-aminophenoxy) benzene (TPE-M) monomers in N-methylpyrrolidone (NMP) to obtain a prepolymer for later use; the molar ratio is 1: 1;
(2) adding weighed bisphenol A type diether dianhydride (BPADA) and/or 4,4' -oxydiphthalic anhydride (ODPA) monomers into the prepolymer obtained in the first step, wherein the weight ratio of the BPADA to the TPE-M is 1:1 (the molar ratio of the BPADA to the TPE-M is 51:50), uniformly mixing, polymerizing for at least 10 hours at the temperature of 15-45 ℃ under the atmosphere of normal pressure and nitrogen protection, and adding NMP to adjust the viscosity to obtain a target product, wherein the solid content is 20-30 wt%, and the viscosity is 30000-40000 cps.
Wherein the 1, 3-bis (4-aminophenoxy) benzene (TPE-R) is a product of Shanghai Gu Chuang chemical new material company Limited, the molecular weight is 292.33, the purity is more than or equal to 99%, the melting point is 115-118 ℃, and the metal ion content (Ca, Fe, Cu) is less than or equal to 2ppm each. 4,4' -oxydiphthalic anhydride (ODPA) is a product of Shanghai solid wound new chemical material limited company, the purity is more than or equal to 99.2 percent, the melting point is 227-230 ℃, and the metal ion content (K, Ca, Na, Fe, Cu) is less than or equal to 2ppm each. The 1, 3-bis (3-aminophenoxy) benzene (TPE-M) is a product of sunshine pharmaceutical industry limited company in Changzhou city, the purity is more than or equal to 99 percent, and the melting point is more than or equal to 105 ℃. Bisphenol A type diether dianhydride (BPADA) is a product of sunshine pharmaceutical industry limited company in Changzhou city, the purity is more than or equal to 99 percent, and the melting point is 188-192 ℃.
In some embodiments of the present invention, the inorganic filler is selected from one or more of nano silica, silica micropowder, molybdenum disulfide, carbon fiber; preferably, the particle size is not higher than 10 μm; preferably, the surface is coated with a silane coupling agent.
Preferably, Polytetrafluoroethylene (PTFE) or a copolymer (PFA) of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene is used as a matrix resin, N-methyl pyrrolidone (NMP) solvent and a fluorine-containing compound dispersing agent are sequentially added, after uniform stirring, a filter screen of 25-35 mu m (500-600 meshes) is used for filtering the mixed glue solution for 2-3 times, the viscosity and the fineness of the mixed glue solution are tested, wherein the viscosity is less than or equal to 500cps, the fineness is less than or equal to 7 mu m, then the weighed inorganic filler and the weighed organic polymer are added into the filtered mixed glue solution, and the mixture is continuously stirred uniformly for later use. And controlling the final viscosity of the mixed glue solution to be 2500-7500 cps.
In the application, inorganic filler coated by a silane coupling agent is added into a glue solution raw material, the filler has good compatibility in a fluorine-containing compound (polymer resin), the roughness between a fluorine material (namely a fluorine-containing glue layer) and an MPI (substrate) interface can be increased by the filler, specific inorganic filler with high surface energy, easy bonding and the like is added in a high-temperature melting process (comprising a sintering stage and a pressing stage), an easy-bonding modified layer is formed on the surface of the fluorine material after cooling, the interface bonding force between the fluorine material and the MPI of the substrate and between the fluorine material and a high-frequency copper foil is increased, the interface compactness is improved, the contact area between the MPI and external water molecules is reduced, and the water absorption of an integral dielectric layer is reduced. In addition, in the application, the thermoplastic polyimide polymer synthesized by the fluorine-containing dianhydride monomer is added into the fluorine-containing compound (polymer resin), so that the dielectric constant and the dielectric loss are low, the water absorption rate is extremely low, and meanwhile, the structural characteristics of the thermoplastic polyimide further enhance the adhesion of the mixed resin and reduce the porosity among the interfaces of the composite material, so that the water absorption rate of the fluorine material dielectric layer is effectively reduced.
<Coating of>
In the invention, the glue solution in the step (1) is coated on the upper surface and the lower surface of a base material (such as an MPI film) at first, and the solvent is dried.
Further preferably, the temperature in the coating is 120-180 ℃; preferably, the linear speed of the coating is controlled to be 2-5 m/min;
further preferably, the temperature parameters of the coater are set to three zones, namely, an elevated temperature zone, a high temperature zone and a buffer zone. The temperature of the heating area is set to be 70-140 ℃, the length of the oven is 4m, and the heating area is mainly used for preheating and shaping glue solution, and volatilizing impurities and solvents; the temperature of the high-temperature area is set to be 150-160 ℃, the length of the oven is 4m, and the oven is mainly used for solvent volatilization and surface drying; the temperature of the buffer area is set to be 120-140 ℃, the length of the oven is 4m, and the buffer area is mainly used for eliminating thermal stress and volatilizing residual solvent.
<Sintering>
And (3) sintering the base material layer coated with the glue solution in the step (2) to be pressed by the copper foil, wherein the sintering linear speed is preferably 0.4-0.8 m/min.
In some embodiments, the sintering process in step (3) includes a preheating process, a high-temperature sintering process, and a temperature-reducing annealing process.
In some preferred embodiments, the temperature in the preheating process is set to be 100-300 ℃, the length of the oven is 3m, and the preheating process is mainly used for presintering and volatilization of impurities such as water vapor and the like; the temperature in the high-temperature sintering process is more than or equal to 315 ℃, the temperature is preferably 310-380 ℃, the length of an oven is 3m, the high-temperature sintering process is mainly used for melting granular fluorine materials into a film shape, and the high-temperature sintering time is not less than 15 min; the temperature in the cooling and annealing process is set to be 50-300 ℃, and the cooling and annealing process is mainly used for thermal stress relief and cooling forming; wherein the temperature gradient between adjacent drying ovens of each section is preferably less than or equal to 50 ℃.
<Pressing together>
In the application, the sintered fluorine material film and the high-frequency copper foil are pressed under the conditions of high temperature and high pressure to prepare the fluorine material flexible copper clad laminate.
In some embodiments, the copper foil for lamination is one of rolled copper or electrolytic copper.
Preferably, the smooth surface roughness of the copper foil is not more than 1.5 μm; further preferably, the surface roughness thereof is not more than 1.0. mu.m.
Preferably, the pressing temperature is 320-370 ℃.
Preferably, the pressing force of the pressing is not less than 3 Mpa.
Preferably, the pressing time is not shorter than 15 min.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Example 1
The embodiment provides a low-water-absorption flexible copper-clad plate made of fluorine materials, which comprises a substrate layer 6, an upper copper layer 1 and a lower copper layer 4, wherein the upper surface and the lower surface of the substrate layer 6 are coated with an upper fluorine-containing glue layer 5 and a lower fluorine-containing glue layer 7; the material of the substrate layer 6 is Modified Polyimide (MPI) and SKC, the mark FG050 is selected. The upper copper layer 1 and the lower copper layer 4 have the same thickness of 12 μm, the roughness Rz is 1.0 μm, the upper fluorine-containing adhesive layer 5 and the lower fluorine-containing adhesive layer 7 have the same thickness of 25 μm, and the base material layer (modified polyimide MPI)6 has a thickness of 25 μm.
The preparation method of the low-water absorption fluoride flexible copper clad laminate comprises the following steps:
(1) preparing glue solution: adding a fluorine-containing compound into a solvent, adding a compound dispersing agent, an inorganic filler and thermoplastic polyimide, and stirring and mixing to obtain a glue solution; wherein the mixture ratio and the raw material components are as follows: 40 parts of copolymer of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene (manufacturer China, brand DS705, melt flow rate of 21.2g/10min and water content of less than or equal to 0.008%), 40 parts of N-methyl pyrrolidone (general industrial grade), 4 parts of fluorine-containing compound dispersing agent (manufacturer ancient times, brand FT-71FL, solid content of 48.9%, specific gravity of 1.092), 10 parts of thermoplastic polyimide gum (self-made, solid content of 25%, viscosity of 30000-40000 cps), and 1.5 parts of silicon micropowder (manufacturer brocade silicon, brand Q029, dielectric constant of 3.8, specific gravity of 2.2 +/-0.1 g/cm, water content of less than or equal to 0.2%, and thermal expansion coefficient of 0.4ppm/° C).
(2) Coating: coating the glue solution obtained in the step (1) on the upper surface and the lower surface of the base material layer, and drying the solvent; wherein the coating parameters are shown in table 1;
TABLE 1
Figure BDA0003176388050000091
(3) And (3) sintering: sintering the base material layer coated with the glue solution in the step (2), wherein the sintering temperature is 100-380 ℃; the sintering parameters are shown in the table 2;
TABLE 2
Figure BDA0003176388050000092
(4) And (3) laminating: and (4) carrying out copper foil laminating on the substrate layer sintered in the step (3) to obtain the low-water-absorption fluorine material flexible copper-clad plate. The pressing parameters are shown in table 3;
TABLE 3
Pressing temperature/. degree.C Compressive force/Mpa tension/N of copper foil Film tension/N Line speed/m/min
To-be-laminated base material 350 3.5 12 8 0.8
Example 2
The embodiment provides a low-water-absorption flexible copper-clad plate made of fluorine materials, which comprises a substrate layer 6, an upper copper layer 1 and a lower copper layer 4, wherein the upper surface and the lower surface of the substrate layer 6 are coated with an upper fluorine-containing glue layer 5 and a lower fluorine-containing glue layer 7; the material of the substrate layer 6 is Modified Polyimide (MPI) selected from SKC under the designation FG 05. The upper copper layer 1 and the lower copper layer 4 have the same thickness of 12 μm, the roughness Rz is 1.0 μm, the upper fluorine-containing adhesive layer 5 and the lower fluorine-containing adhesive layer 7 have the same thickness of 25 μm, and the base material layer (modified polyimide MPI)6 has a thickness of 25 μm.
The preparation method of the low-water-absorption flexible copper-clad plate is different from that of the embodiment 1 in the formula of glue solution, wherein the glue solution formula in the embodiment is composed of 40 parts of DS705, 40 parts of NMP, 4 parts of FT-71FL, 15 parts of thermoplastic polyimide and 1.5 parts of silica micropowder (parts by weight).
Example 3
The embodiment provides a low-water-absorption flexible copper-clad plate made of fluorine materials, which comprises a substrate layer 6, an upper copper layer 1 and a lower copper layer 4, wherein the upper surface and the lower surface of the substrate layer 6 are coated with an upper fluorine-containing glue layer 5 and a lower fluorine-containing glue layer 7; the material of the substrate layer 6 is Modified Polyimide (MPI) selected from SKC under the designation FG 05. The upper copper layer 1 and the lower copper layer 4 have the same thickness of 12 μm, the roughness Rz is 1.0 μm, the upper fluorine-containing adhesive layer 5 and the lower fluorine-containing adhesive layer 7 have the same thickness of 25 μm, and the base material layer (modified polyimide MPI)6 has a thickness of 25 μm.
The preparation method of the low-water-absorption flexible copper-clad plate is different from that of the embodiment 1 in the formula of glue solution, wherein the glue solution formula in the embodiment is composed of 40 parts of DS705, 40 parts of NMP, 4 parts of FT-71FL, 20 parts of thermoplastic polyimide and 1.5 parts of silica micropowder (parts by weight).
Example 4
The embodiment provides a low-water-absorption flexible copper-clad plate made of fluorine materials, which comprises a substrate layer 6, an upper copper layer 1 and a lower copper layer 4, wherein the upper surface and the lower surface of the substrate layer 6 are coated with an upper fluorine-containing glue layer 5 and a lower fluorine-containing glue layer 7; the material of the substrate layer 6 is Modified Polyimide (MPI) selected from SKC under the designation FG 05. The upper copper layer 1 and the lower copper layer 4 have the same thickness of 12 μm, the roughness Rz is 1.0 μm, the upper fluorine-containing adhesive layer 5 and the lower fluorine-containing adhesive layer 7 have the same thickness of 25 μm, and the base material layer (modified polyimide MPI)6 has a thickness of 25 μm.
The preparation method of the low-water-absorption flexible copper-clad plate is different from that of the embodiment 1 in the formula of glue solution, wherein the glue solution formula in the embodiment is composed of 40 parts of DS705, 40 parts of NMP, 4 parts of FT-71FL, 10 parts of thermoplastic polyimide and 2.0 parts of silica micropowder (parts by weight).
Example 5
The embodiment provides a low-water-absorption flexible copper-clad plate made of fluorine materials, which comprises a substrate layer 6, an upper copper layer 1 and a lower copper layer 4, wherein the upper surface and the lower surface of the substrate layer 6 are coated with an upper fluorine-containing glue layer 5 and a lower fluorine-containing glue layer 7; the material of the substrate layer 6 is Modified Polyimide (MPI) selected from SKC under the designation FG 05. The upper copper layer 1 and the lower copper layer 4 have the same thickness of 12 μm, the roughness Rz is 1.0 μm, the upper fluorine-containing adhesive layer 5 and the lower fluorine-containing adhesive layer 7 have the same thickness of 25 μm, and the base material layer (modified polyimide MPI)6 has a thickness of 25 μm.
The preparation method of the low-water-absorption flexible copper-clad plate is different from that of the embodiment 1 in the formula of glue solution, wherein the glue solution formula in the embodiment is composed of 40 parts of DS705, 40 parts of NMP, 4 parts of FT-71FL, 10 parts of thermoplastic polyimide and 2.5 parts of silica micropowder (parts by weight).
Comparative example 1
The comparative example provides a low-water-absorption flexible copper-clad plate made of fluorine materials, which comprises a substrate layer 6, an upper copper layer 1 and a lower copper layer 4, wherein the upper surface and the lower surface of the substrate layer 6 are coated with an upper fluorine-containing glue layer 5 and a lower fluorine-containing glue layer 7; the material of the substrate layer 6 is Modified Polyimide (MPI) selected from SKC under the designation FG 05. The upper copper layer 1 and the lower copper layer 4 have the same thickness of 12 μm, the roughness Rz is 1.0 μm, the upper fluorine-containing adhesive layer 5 and the lower fluorine-containing adhesive layer 7 have the same thickness of 25 μm, and the base material layer (modified polyimide MPI)6 has a thickness of 25 μm.
The preparation method of the low-water-absorption flexible copper-clad plate is different from that of the embodiment 1 in the formula of glue solution, wherein the glue solution in the embodiment comprises 40 parts of DS705, 40 parts of NMP, 4 parts of FT-71FL and 1.5 parts of silica micropowder (by weight).
Comparative example 2
The comparative example provides a low-water-absorption flexible copper-clad plate made of fluorine materials, which comprises a substrate layer 6, an upper copper layer 1 and a lower copper layer 4, wherein the upper surface and the lower surface of the substrate layer 6 are coated with an upper fluorine-containing glue layer 5 and a lower fluorine-containing glue layer 7; the material of the substrate layer 6 is Modified Polyimide (MPI) selected from SKC under the designation FG 05. The upper copper layer 1 and the lower copper layer 4 have the same thickness of 12 μm, the roughness Rz is 1.0 μm, the upper fluorine-containing adhesive layer 5 and the lower fluorine-containing adhesive layer 7 have the same thickness of 25 μm, and the base material layer (modified polyimide MPI)6 has a thickness of 25 μm.
The preparation method of the low-water-absorption flexible copper-clad plate is different from that of the embodiment 1 in the formula of glue solution, wherein the glue solution in the embodiment comprises 40 parts of DS705, 40 parts of NMP, 4 parts of FT-71FL and 10 parts of thermoplastic polyimide (by weight).
Performance testing
The applicant performs the performance tests of water absorption, peel strength, dielectric constant (Dk), dielectric loss (Df), tensile strength, elongation, dimensional stability, soldering resistance and the like on the fluorine flexible copper clad laminate materials prepared in the above examples and comparative examples by using the test methods specified in industry IPC-TM-650, jis c6471 and SPDR, and the test results are shown in the following table 4:
TABLE 4 Performance test
Figure BDA0003176388050000111
Figure BDA0003176388050000121
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. The low-water-absorption flexible copper-clad plate is characterized by comprising a substrate layer and a copper layer, wherein the upper surface and the lower surface of the substrate layer are coated with fluorine-containing glue layers; the material of the substrate layer is modified polyimide.
2. The low water absorption fluoride material flexible copper-clad plate according to claim 1, wherein the surface tension of the substrate layer is not less than 60 dyn; preferably, the dielectric loss of the substrate layer is not higher than 0.0045.
3. The low water absorption fluoride flexible copper clad laminate according to claim 1 or 2, wherein the surface roughness Rz of the copper layer is not higher than 1.5 μm.
4. The low-water absorption fluoride flexible copper-clad plate according to claim 3, wherein the thickness of the copper layer is 5-25 μm; preferably, the thickness of the fluorine-containing adhesive layer is 5-50 μm; preferably, the thickness of the base material layer is 5-80 μm.
5. The preparation method of the low water absorption fluoride material flexible copper clad laminate according to any one of claims 1 to 4, characterized by comprising the following steps:
(1) preparing glue solution: adding a fluorine-containing compound into a solvent, adding a compound dispersing agent, an inorganic filler and thermoplastic polyimide, and stirring and mixing to obtain a glue solution;
(2) coating: coating the glue solution obtained in the step (1) on the upper surface and the lower surface of the base material layer, and drying the solvent; preferably, the temperature in the coating is 120-180 ℃; preferably, the linear speed of the coating is controlled to be 2-5 m/min;
(3) and (3) sintering: sintering the base material layer coated with the glue solution in the step (2), wherein the sintering temperature is 100-380 ℃;
(4) and (3) laminating: carrying out copper foil laminating on the substrate layer sintered in the step (3), wherein the laminating temperature is 320-370 ℃, and the laminating pressure is not lower than 3Mpa, so as to obtain the low-water-absorption fluorine material flexible copper clad laminate; further preferably, the dwell time in the pressing is not less than 15 min.
6. The method for preparing the low water absorption fluorine material flexible copper clad laminate according to claim 5, wherein the fluorine-containing compound is selected from one or more of polytetrafluoroethylene, a copolymer of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene, a tetrafluoroethylene-perfluoromethyl vinyl ether copolymer and an ethylene-tetrafluoroethylene copolymer.
7. The preparation method of the low water absorption fluorine material flexible copper clad laminate according to claim 5, wherein the thermoplastic polyimide molecular structure contains at least one of imide group, ether group structure and alkyl group structure; preferably, the viscosity of the thermoplastic polyimide is 20000 to 40000 cps.
8. The method for preparing the low water absorption fluoride flexible copper clad laminate according to claim 7, wherein the raw materials for preparing the thermoplastic polyimide comprise 1, 3-bis (3-aminophenoxy) benzene and/or 1, 3-bis (4-aminophenoxy) benzene, bisphenol A type diether dianhydride and/or 4,4' -oxydiphthalic anhydride.
9. The preparation method of the low water absorption fluoride material flexible copper clad laminate according to any one of claims 5 to 8, wherein the inorganic filler is selected from one or more of nano silica, silica micropowder, molybdenum disulfide and carbon fiber; preferably, the particle size is not higher than 10 μm; preferably, the surface is coated with a silane coupling agent.
10. The preparation method of the low water absorption fluoride flexible copper clad laminate according to claim 5, wherein the sintering process in the step (3) comprises a preheating process, a high temperature sintering process and a cooling annealing process; the temperature of the high-temperature sintering process is more than or equal to 315 ℃, and the high-temperature sintering time is not less than 15 min.
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